CN103387840A - Method for preparing biofuel through graded catalytic liquefaction of straw - Google Patents
Method for preparing biofuel through graded catalytic liquefaction of straw Download PDFInfo
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- CN103387840A CN103387840A CN2013102599925A CN201310259992A CN103387840A CN 103387840 A CN103387840 A CN 103387840A CN 2013102599925 A CN2013102599925 A CN 2013102599925A CN 201310259992 A CN201310259992 A CN 201310259992A CN 103387840 A CN103387840 A CN 103387840A
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- stalk
- bio oil
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- catalyst
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Abstract
The invention discloses a method for preparing biofuel through graded catalytic liquefaction of straw. The method uses straw as a raw material, and liquefies the straw into biofuel through graded alcoholysis under the catalysis of magnetic catalysts, CaO-Al2O3-Fe3O4. Under the catalysis of simple lower alcohols and the mentioned catalysts, the straw reacts at a set temperature for a period of time to obtain the biofuel and residue. The residue is dried, weighed, put in an autoclave with lower alcohols, and heated to a next temperature point for reactions for the same period of time. The above operations are repeated successively. The method achieves recycling of the catalysts on one hand, and improves the utilization rate and the biofuel yield rate of biomass on the other hand.
Description
Technical field
The present invention relates to a kind of preparation method of bio oil, specifically a kind of stalk classification catalytic liquefaction prepares the method for bio oil, belongs to biomass efficient and utilizes technical field.
Background technology
Biomass are the most promising a kind of renewable resourcess that can prepare fuel and industrial chemicals on the earth.China's biomass resource is abundant, and only the agricultural crop straw annual production just reaches 700,000,000 tons, accounts for 30% of world's stalk ultimate production.In stalk, organic content approximately 15%, and contains the various trace elements such as nitrogen, phosphorus and potassium; Mierocrystalline cellulose in stalk, hemicellulose, xylogen, protein etc. can be decomposed by microorganism, also can obtain industrial chemicals or be processed into feed through thermochemical method.Yet, only have the small portion stalk to be regarded feed or fertilizer in rural area, major part is all by on-site incineration.On the one hand, the on-site incineration of stalk is owing to discharging a large amount of carbon monoxide, oxynitride, carbonic acid gas and macrobead dust etc. in combustion processes, and seriously reduces the quality of atmosphere.On the other hand, the on-site incineration of stalk can burn soil, disperses soil moisture, accelerates organic volatilization, makes soil aggregate be destroyed and the havoc Soil structure; Simultaneously, the on-site incineration of stalk causes the waste of a large amount of renewable energy sources.So the most urgent task is industrial chemicals or the high substituted liquid fluid fuel (bio oil) of energy density that biomass straw is converted on a large scale, efficiently high added value, easily stores, easily transports at present.
At present, the difficult point of biomass liquefaction reaction is that liquefied fraction is lower and the bio oil product quality is not high, and viscosity is large, unstable chemcial property, acid number is high, catalyzer add the solution that will help these problems.The shortcoming of these catalyzer: acid base catalysator has very strong corrodibility to conversion unit, with bio oil, mixes, and has increased bio-oil upgrading and purification step; Loaded catalyst is expensive, with residue, can't separate, and can not realize the recycling of catalyzer.
Our seminar adopts coprecipitation method with CaO, Al before this
2O
3And Fe
3O
4Immerse the NaOH aqueous solution, then magnetic catalyst is prepared in high-temperature calcination in retort furnace, and this catalyzer is used to the overcritical alcoholysis of catalysis straw under certain condition
[6-8].Reach more than 95% although obtain the bio oil productive rate, we adopt the formula that calculates the bio oil productive rate to be:
Y L =
m L /
m Stalk , daf * 100%, in this alcoholysis process, solvent has also participated in catalyzed reaction, but its quality is not entered the calculation of yield formula by Bands, so the productive rate of bio oil is higher.If the solvent quality that will participate in is brought formula into
Y L =
∑ m L / (
m Stalk , daf +
m Participate in the solvent of reaction ), the bio oil productive rate is 50.6 %, although improved oil yield rate, total oil yield rate is not also very high.(note: the productive rate of bio oil and residue is used respectively
Y L With
Y S Expression, calculation formula is:
Y L =
∑ m L / (
m Stalk , daf +
m Participate in the solvent of reaction ),
Y S =
m S / (
m Stalk , daf +
m Participate in the solvent of reaction ), wherein
m L The quality of the product liquid that obtains for current temperature of reaction point,
m S For the quality of the residue that obtains after alcoholysis reaction,
m Stalk , daf For carrying out the stalk quality of the ashless drying that alcoholysis reaction adds,
m Participate in the solvent of reaction For participating in the quality of the solvent that reacts.
Summary of the invention
Problem for above-mentioned prior art exists, the invention provides a kind of stalk classification catalytic liquefaction and prepare the method for bio oil, improves on the one hand liquefied fraction and the oil yield rate of stalk, realizes on the other hand the recycling of catalyzer.Simultaneously, adopt the method for classification alcoholysis, realize at utmost utilizing liquefaction of corn straw to obtain bio oil.
To achieve these goals, the technical solution used in the present invention is: comprise the following steps:
(1) stalk, simple low-carbon alcohol solvent and magnetic catalyst are put into autoclave by a certain percentage, be heated to rapidly assigned temperature and keep certain hour, obtain liquefaction of corn straw product-bio oil and residue after reaction;
(2) residue is 100
oC-105
oWeigh after vacuum-drying for some time under C;
(3) filtrate is distilled, and is standing, and the product liquid that finally obtains is called " bio oil ", and it is weighed;
(4) then will obtain residue classification catalysis and namely residue, simple low-carbon alcohol solvent and homemade magnetic catalyst be put into autoclave by a certain percentage, be heated to rapidly assigned temperature and keep certain hour, obtain liquefied product-bio oil and residue after reaction, then repeating step (2) and step (3);
Preferably, the low-carbon alcohol solvent that adds in described step (1) is C1-C5 alcohol;
The stalk quality that adds and the ratio of catalyst quality are 10:1-30:1, and when the ratio of stalk quality and catalyst quality was 25:1, oil yield rate was the highest.
Described magnetic catalyst CaO-Al
2O
3-Fe
3O
4The preparation method as follows: at N
2Under atmosphere, with FeSO
47H
2O, Fe
2(SO
4)
3Be dissolved in certain proportion in rare HCl solution.Under vigorous stirring, above-mentioned solution is dropwise splashed in certain density NaOH solution.After reaction finishes, Fe
3O
4Be deposited under magneticaction and be separated, with the above-mentioned neutrality that is precipitated to of deionized water wash, then with product 80
oDry, cooling, standby in the C baking oven.Add by a certain percentage Ca (Ac) in the magnetotropism matrix
2The Al of the aqueous solution and activation
2O
3, stir it is fully mixed, and ultrasonic, standing 4 h of difference.Throw out is in 80
oCVacuum-drying 12 h, finally at N
2600-800 in the atmosphere tube type stove
oCCalcining 2-4 h, obtain CaO/Al
2O
3/ Fe
3O
4Magnetic catalyst.
The present invention adopts the method liquefied straw of classification alcoholysis, makes the liquefied fraction of stalk and oil yield rate increase, simultaneously with magnetic catalyst CaO-Al
2O
3-Fe
3O
4Use in the classification alcoholysis liquefaction of stalk, the productive rate of bio oil improves greatly, the magnetic catalyst CaO-Al that is recovered to
2O
3-Fe
3O
4The catalytic effect of recycling is still fine.
Compared with prior art the invention has the advantages that: 1. the classification alcoholysis of stalk, farthest realized straw utilization, under different condition, the yield of bio oil is 72.5%-96.8%, and lot of documents show stalk through the bio oil yield that obtains of liquefaction once below 60%
[1-5].The magnetic catalyst of this patent preparation is used for an alcoholysis of stalk, the yield that obtains bio oil is 50.2%-64.5%.2, Fe
3O
4Magnetic matrix in preparation process and the later stage prepare in the process of loading type magnetic catalyst all easily oxidized by high-temperature calcination as magnetic matrix; On the other hand, the solubleness of CaO in water seldom, and is disperseed inhomogeneously in water, and the solubleness of calcium acetate in water is very large, and at high temperature calcining and decomposing is CaO.So the magnetic loading type catalyzer of this patent preparation is at first to prepare magnetic matrix Fe under inert atmosphere
3O
4, then with Al
2O
3And Fe
3O
4Be immersed in the certain density calcium acetate aqueous solution, oven dry, roasting obtain magnetic loading type catalyzer CaO-Al under inert atmosphere
2O
3-Fe
3O
4, the magnetic catalyst CaO-Al that then will prepare
2O
3-Fe
3O
4Use in the alcoholysis liquefaction of stalk, improved the liquefied fraction of stalk, by the experiment effect of specific embodiment to recently seeing, adding the quality of stalk and the mass ratio of magnetic catalyst is in the situation of 10:1,15,20:1 and 30:1, the bio oil productive rate of stalk is the plateau of 85%-88%, but when the mass ratio of the quality that adds stalk and magnetic catalyst is 25:1, find that stalk obtains maximum depolymerization, make the liquefied fraction of stalk almost reach 100%, the productive rate of bio oil reaches more than 96%, particularly the oil generation productive rate of straw is maximum, reaches 96.8%.
Embodiment
Embodiment 1: the present embodiment is that to add the quality of stalk and the mass ratio of magnetic catalyst be the embodiment of 10:1.
The making method of magnetic catalyst: at N
2Under atmosphere, with 4.4gFeSO
47H
2O, 6.4g Fe
2(SO
4)
3Be dissolved in the 25mL deionized water with the HCl solution of 0.85mL12 mol/L.At N
2Vigorous stirring under atmosphere, dropwise splash into above-mentioned solution in the NaOH solution of 250mL0.5mol/L.After reaction finishes, Fe
3O
4Be deposited under magneticaction and be separated, with 200mL deionized water wash above-mentioned precipitation four times, then with product 80
oDry, cooling, standby in the C baking oven, add 2.79g Ca (Ac) in the magnetotropism matrix
2H
2O is made into the aqueous solution of 10mL and the Al of 1.64g activation
2O
3, stir it is fully mixed, and ultrasonic, standing 4 h of difference.Throw out is in 80
oCVacuum-drying 12 h, finally at N
2600-800 in the atmosphere tube type stove
oCCalcining 2-4 h, obtain CaO-Al
2O
3-Fe
3O
4Magnetic catalyst.
With the 2g rice straw, 0.2g magnetic catalyst CaO-Al
2O
3-Fe
3O
4Add in the magnetic agitation autoclave of 200 mL with 60 mL dehydrated alcohols, be heated to rapidly 100
oC, keep 0.5 h at this temperature.After alcoholysis reaction finished, with the product decompress filter after taking out, residue was colourless to filtrate with the dehydrated alcohol repetitive scrubbing.Residue is in moisture eliminator after dry 24 h, in 105
oC vacuum-drying 40 min, then weigh.Filtrate is distilled, and removes dehydrated alcohol, obtains bio oil, and it is weighed.The residue that then will obtain adds in the magnetic agitation autoclave of 200 mL, adds a certain amount of dehydrated alcohol, and keeping solid-to-liquid ratio is 1:30 g/mL, slowly is warming up to 150
oC, keep 0.5 h at this temperature, obtain residue and filtrate after alcoholysis is completed, the like, 200
oC obtains residue and filtrate, 250
oC obtains residue and filtrate, 300
oC obtains residue and filtrate.The productive rate that obtains bio oil is 85.3%, and the residue rate is 15.5%.Using under similar circumstances the productive rate of the bio oil that corn stalk obtains as raw material is 84.2%, and the residue rate is 15.1%, and the bio oil productive rate that uses rice straw to obtain as raw material is 83.9%, and the residue rate is 15.9%.
Comparative Examples 1
Do not adding magnetic catalyst CaO-Al
2O
3-Fe
3O
4,Other steps and embodiment 1 are all in the same situation, and using straw is 30.1% as the productive rate that raw material obtains bio oil, and the residue rate is 58.3%.Using cornstalk is 28.5% as the productive rate that raw material obtains bio oil, and the residue rate is 60.3%, and using rice straw is 25.6% as the productive rate that raw material obtains bio oil, and the residue rate is 67.8%.
Comparative Examples 2
In the situation that there is no the classification alcoholysis, that is: with the 2g rice straw, 0.2g magnetic catalyst CaO-Al
2O
3-Fe
3O
4Add in the magnetic agitation autoclave of 200 mL with 60 mL dehydrated alcohols, be heated to rapidly 100
oC, keep 0.5 h at this temperature.After alcoholysis reaction finished, with the product decompress filter after taking out, residue was colourless to filtrate with the dehydrated alcohol repetitive scrubbing.Residue is in moisture eliminator after dry 24 h, in 105
oC vacuum-drying 40 min, then weigh.Filtrate is distilled, and removes dehydrated alcohol, and the productive rate that obtains bio oil is 64.6 %, and the residue rate is 24.5%.
Embodiment 2: the present embodiment is that to add the quality of stalk and the mass ratio of magnetic catalyst be the embodiment of 15:1.
The making method of magnetic catalyst is with embodiment 1, with the 3g straw, and 0.2g magnetic catalyst CaO-Al
2O
3-Fe
3O
44Add in the magnetic agitation autoclave of 200 mL with 90 mL dehydrated alcohols, other implementation steps are as shown in example 1.The productive rate that obtains bio oil is 87.4%, and the residue rate is 12.8%.Using under similar circumstances the productive rate of the bio oil that corn stalk obtains as raw material is 87.2%, and the residue rate is 12.1%, and the bio oil productive rate that uses rice straw to obtain as raw material is 86.9%, and the residue rate is 13.5%.
Embodiment 3: the present embodiment is that to add the quality of stalk and the mass ratio of magnetic catalyst be the embodiment of 20:1.
The making method of magnetic catalyst is with embodiment 1, with the 2g straw, and 0.1g magnetic catalyst CaO-Al
2O
3-Fe
3O
4Add in the magnetic agitation autoclave of 200 mL with 60 mL dehydrated alcohols, other implementation steps are as shown in example 1.The productive rate that obtains bio oil is 86.9%, and the residue rate is 5.7%.Using under similar circumstances the productive rate of the bio oil that corn stalk obtains as raw material is 86.2%, and the residue rate is 6.1%, and the bio oil productive rate that uses rice straw to obtain as raw material is 85.9%, and the residue rate is 7.9%.
Embodiment 4: the present embodiment is that to add the quality of stalk and the mass ratio of magnetic catalyst be the embodiment of 25:1.
The making method of magnetic catalyst is with embodiment 1, with the 5g straw, and 0.2g magnetic catalyst CaO-Al
2O
3-Fe
3O
4Add in the magnetic agitation autoclave of 1000 mL with 150 mL dehydrated alcohols, other implementation steps are as shown in example 1.The productive rate that obtains bio oil is 96.8%, and the residue rate is 2.1%.Using under similar circumstances the productive rate of the bio oil that corn stalk obtains as raw material is 96.5%, and the residue rate is 3.1%, and the bio oil productive rate that uses rice straw to obtain as raw material is 96.1%, and the residue rate is 3.9%.
Embodiment 5: the present embodiment is that to add the quality of stalk and the mass ratio of magnetic catalyst be the embodiment of 30:1.
The making method of magnetic catalyst is with embodiment 1, with the 3g straw, and 0.1g magnetic catalyst CaO-Al
2O
3-Fe
3O
4Add in the magnetic agitation autoclave of 200 mL with 90 mL dehydrated alcohols, other implementation steps are as shown in example 1.The productive rate that obtains bio oil is 86.1%, and the residue rate is 11.5%.Using under similar circumstances the productive rate of the bio oil that corn stalk obtains as raw material is 85.2%, and the residue rate is 13.1%, and the bio oil productive rate that uses rice straw to obtain as raw material is 84.9%, and the residue rate is 13.9%.
The mass ratio that adds in sum the quality of stalk and magnetic catalyst is that the embodiment of 25:1 is best effect of the present invention, particularly utilizes in the situation of straw, and the bio oil productive rate is greatly improved.
Claims (5)
1. a stalk classification catalytic liquefaction prepares the method for bio oil, it is characterized in that comprising the following steps:
(1) stalk, simple low-carbon alcohol solvent and magnetic catalyst are put into autoclave by a certain percentage, be heated to rapidly assigned temperature and keep certain hour, obtain liquefaction of corn straw product-bio oil and residue after reaction;
(2) residue is 100
oC-105
oWeigh after vacuum-drying for some time under C;
(3) filtrate is distilled, and is standing, and the product liquid that finally obtains is called " bio oil ", and it is weighed;
(4) then will obtain residue classification catalysis namely residue, simple low-carbon alcohol solvent and magnetic catalyst CaO-Al
2O
3-Fe
3O
4Put into by a certain percentage autoclave, be heated to rapidly assigned temperature and keep certain hour, obtain liquefied product-bio oil and residue after reaction, then repeating step (2) and step (3);
According to claim 1, the stalk classification catalytic liquefaction shown in prepare the method for bio oil, it is characterized in that, the low-carbon alcohol solvent that adds in described step (1) is C1-C5 alcohol;
The stalk quality that adds and the ratio of catalyst quality are 10:1-30:1;
The low-carbon alcohol solvent volume (mL) that adds and the ratio of catalyst quality (g) are 10:1-30:1.
2. the stalk classification catalytic liquefaction shown according to claim 2 prepares the method for bio oil, it is characterized in that,
The ratio of stalk quality and catalyst quality is 25:1;
The ratio of low-carbon alcohol solvent volume (mL) and catalyst quality (g) is 10:1-30:1.
3. the stalk classification catalytic liquefaction shown according to claim 2 prepares the method for bio oil, it is characterized in that, the low-carbon alcohol solvent that adds in described step (4) is C1-C5 alcohol;
The residue quality that adds and the ratio of catalyst quality are 10:1-30:1;
The low-carbon alcohol solvent volume (mL) that adds and the ratio of catalyst quality (g) are 10:1-30:1.
4. prepare the method for bio oil by the stalk classification catalytic liquefaction shown in claim 1, it is characterized in that, described magnetic catalyst CaO-Al
2O
3-Fe
3O
4Be prepared as follows: at N
2Under atmosphere, with FeSO
47H
2O, Fe
2(SO
4)
3Ratio with 2:3 is dissolved in rare HCl solution, under vigorous stirring, above-mentioned solution dropwise splashed in certain density NaOH solution, and after reaction finishes, Fe
3O
4Be deposited under magneticaction and be separated, with the above-mentioned neutrality that is precipitated to of deionized water wash, then with product 80
oDry, cooling, standby in the C baking oven, add by a certain percentage Ca (Ac) in the magnetotropism matrix
2The Al of the aqueous solution and activation
2O
3, stir it is fully mixed, and ultrasonic, standing 4 h of difference.
5. throw out is in 80
oC vacuum-drying 12 h, finally at N
2600-800 in the atmosphere tube type stove
oC calcining 2-4 h, obtain CaO-Al
2O
3-Fe
3O
4Magnetic catalyst.
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|---|---|---|---|
| CN201310259992.5A CN103387840B (en) | 2013-06-27 | 2013-06-27 | Method for preparing biofuel through graded catalytic liquefaction of straw |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310259992.5A CN103387840B (en) | 2013-06-27 | 2013-06-27 | Method for preparing biofuel through graded catalytic liquefaction of straw |
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| Publication Number | Publication Date |
|---|---|
| CN103387840A true CN103387840A (en) | 2013-11-13 |
| CN103387840B CN103387840B (en) | 2015-07-08 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178198A (en) * | 2014-07-14 | 2014-12-03 | 上海昆仑赫巴农业科技有限公司 | Method and equipment for producing liquefied straw oil |
| CN105363450A (en) * | 2014-09-01 | 2016-03-02 | 中科合成油技术有限公司 | Hydro-liquefied iron-based catalyst containing carbon materials and preparation method and application of hydro-liquefied iron-based catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4935567A (en) * | 1984-11-09 | 1990-06-19 | Agency Of Industrial Science And Technology | Process for liquefying cellulose-containing biomass |
| US5807952A (en) * | 1994-09-19 | 1998-09-15 | Midwest Research Institute | Process for producing phenolic compounds from lignins |
-
2013
- 2013-06-27 CN CN201310259992.5A patent/CN103387840B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4935567A (en) * | 1984-11-09 | 1990-06-19 | Agency Of Industrial Science And Technology | Process for liquefying cellulose-containing biomass |
| US5807952A (en) * | 1994-09-19 | 1998-09-15 | Midwest Research Institute | Process for producing phenolic compounds from lignins |
Non-Patent Citations (1)
| Title |
|---|
| WEN-JUAN XU等: "Supercritical Ethanolysis of Wheat Stalk Powder over CaO/Al2O3 and CaO/Al2O3/Fe3O4", 《ENERGY FUELS》, vol. 24, no. 1, 14 October 2009 (2009-10-14), pages 250 - 252 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178198A (en) * | 2014-07-14 | 2014-12-03 | 上海昆仑赫巴农业科技有限公司 | Method and equipment for producing liquefied straw oil |
| CN104178198B (en) * | 2014-07-14 | 2015-11-04 | 上海昆仑赫巴农业科技有限公司 | Produce method and the device of liquefaction of corn straw oil |
| CN105363450A (en) * | 2014-09-01 | 2016-03-02 | 中科合成油技术有限公司 | Hydro-liquefied iron-based catalyst containing carbon materials and preparation method and application of hydro-liquefied iron-based catalyst |
| CN105363450B (en) * | 2014-09-01 | 2018-01-19 | 中科合成油技术有限公司 | A kind of ferrum-based catalyst of carbon raw material hydrogenation liquefaction and its preparation method and application |
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|---|---|
| CN103387840B (en) | 2015-07-08 |
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